CN102408865A - Double-component polyurethane adhesive and preparation method thereof - Google Patents
Double-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN102408865A CN102408865A CN2011102895065A CN201110289506A CN102408865A CN 102408865 A CN102408865 A CN 102408865A CN 2011102895065 A CN2011102895065 A CN 2011102895065A CN 201110289506 A CN201110289506 A CN 201110289506A CN 102408865 A CN102408865 A CN 102408865A
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Abstract
The invention provides a double-component polyurethane adhesive and a preparation method thereof. The double-component polyurethane adhesive, according to part by weight, comprises component A: 300-800 (preferably 500-700, more preferably 600) parts of styrene grafted polyether polyol, 100-300 (preferably 170-210, more preferably 195) parts of polypropylene glycol PPG400, 100-300 (preferably 170-210, more preferably 195) parts of polypropylene glycol PPG2000, and 1-20 (preferably 3-14) parts of selectively added additives; and component B: 600-800 (preferably 700) parts of imine modified 4,4'-diphenylmethanediisocyanate, and 200-400 (preferably 300) parts of coarse MDI (Diphenylmethanediisocyanate). The polyurethane adhesive has excellent initial cohesive force and excellent toughness; after the adhesive is completely cured, a bonded PP (Poly Propylene) plate can be stripped and repaired, and simultaneously is resistant to water washing; and the adhesive is matched with ink on the PP plate to reach satisfactory surface resistance.
Description
Technical field
The present invention relates to a kind of dual-component polyurethane adhesive and preparation method thereof, especially relate to a kind of dual-component polyurethane adhesive that is used for screen material and preparation method thereof, this tackiness agent cooperates electrically conductive ink can produce satisfactory surface resistivity.
Background technology
The filter screen of conventional electrostatic precipitator comprises the negative plate and the positive plate of parallel alternate setting.This filter screen import and export passage is vertical with the cathode and anode pole plate; Described cathode and anode pole plate shifts to install up and down respectively each other, forms the dish type passage that is cleaned gas flow.Conventional adhesive for polyurethane with the dissolving of the electrically conductive ink on the sheet material, perhaps reacts with printing ink easily, can't produce to reach the surface resistivity that needs.
Bi-component polyurethane adhesive has A component and B component usually.The A component is polyvalent alcohol normally, and the B component is isocyanic ester normally.When needs are bonding, A component and B component are mixed, be applied to then on the base material, solidification takes place between the active hydrogen of free isocyanate groups and polyvalent alcohol, produce bonding.
Because can freely changing prescription, such tackiness agent forms, therefore can be according to the needs adjustment prescription of purposes.In order to improve the surface resistivity of material when bonding of band electrically conductive ink, make it can reach the demand of end-use, the inventor constantly brings forth new ideas, and has obtained a kind of new dual-component polyurethane adhesive.Dual-component polyurethane adhesive of the present invention has the plate adhesion of electrically conductive ink with polylith, forms the filter screen with certain size specification.
Summary of the invention
Technical problem to be solved by this invention is: overcome and adhere to when having the material of conductive ink layer; The undesirable defective of surface resistivity that electrically conductive ink and tackiness agent produce; A kind of dual-component polyurethane adhesive is provided; When it is used on the screen material, can cooperate with electrically conductive ink, (this application requiring surface resistivity is 10 to produce the surface resistivity that meets customer demand
6～10
8Ω).And this tackiness agent has splendid initial adherence power and good toughness, and being convenient to is not simultaneously influenced the sticking power of tackiness agent by the adhesives maintenance of doing over again after the washing.
In order to solve the problems of the technologies described above, dual-component polyurethane adhesive of the present invention, with the polyether glycol of different molecular weight as the A component; With imine modified 4; 4 '-'-diphenylmethane diisocyanate (4,4 '-methylene radical two (phenyl isocyanate), MDI) with thick MDI as the B component.When this dual-component polyurethane adhesive cooperates with electrically conductive ink, can produce the surface resistivity that meets customer demand.
Specifically, the invention provides following technical scheme:
First technical scheme that the present invention adopts is a kind of dual-component polyurethane adhesive to be provided, in weight part; Comprise the A component: styrene-grafted polyether glycol 300-800 part (preferred 500-700 part, more preferably 600 parts), W 166 PPG400 100-300 part (preferred 170-210 part; More preferably 195 parts); Additive 1-20 part (preferred 3-14 part) that W 166 PPG2000 100-300 part (preferred 170-210 part, more preferably 195 parts) and selectivity are added; And B component: imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts).
The used styrene-grafted polyether glycol of the present invention adopts vinylbenzene that polyether glycol is carried out graft modification according to weight part 30-65: 45-60 and obtains; Said polyether glycol is oxyethane, the propylene oxide adduct that glycerine causes, and its repeating unit is
The about 2000g/mol of this styrene-grafted polyether glycol number-average molecular weight.The hydroxyl value of the used styrene-grafted polyether glycol of the present invention is 155mg KOH/g, and viscosity is 2600mPas in the time of 25 ℃, and density is 1.01g/cm in the time of 25 ℃
3
The present invention is used imine modified 4,4 '-'-diphenylmethane diisocyanate be contain 4,4 of carbodiimide and/or uretonimine groups '-diphenylmethanediisocyanate, NCO content is 20%-40%, preferred NCO content is 29.5%.
The present invention is used imine modified 4, and 4 '-'-diphenylmethane diisocyanate can be a synthetic voluntarily, also can be commercial.Its reaction equation is following:
In addition, the diimine group can further obtain uretonimine with excessive isocyanic ester radical reaction.
The used thick MDI of the present invention is poly methylene poly phenyl poly isocyanate (PMDI) and 4; The mixture of 4 '-'-diphenylmethane diisocyanate (MDI); This thick MDI functionality (NCO group) is about 2.6～2.7; Wherein 4,4 '-'-diphenylmethane diisocyanate accounts for 40-60% (preferred about 50%), and NCO content is 30%-32%.The M20S that produces of BASF AG for example.But above-mentioned poly methylene poly phenyl poly isocyanate is made up of homologues such as the methylenediphenyl two isocyanide ester esters of component content modulation, dimethylene triphenyl triisocyanate, trimethylene tetraphenyl tetraisocyanates.
The present invention can also add some the conventional additive that is used for polyurethane adhesive, for example skimmer, catalyzer, water-removal additive, chain extension agent, end-capping reagent, filler, pigment etc. according to applicable cases.
Aforesaid dual-component polyurethane adhesive, in weight part, said additive comprises skimmer 1-3 part (preferred 2 parts), catalyzer 1-3 part (preferred 2 parts) and water-removal additive 4-8 part (preferred 6 parts).
The used skimmer of the present invention is the silicon-type skimmer, and its solvent is C
12-20(petroleum fractions cas:64742-46-7), can be bought the A530 from BYK to isoparaffin.
Catalyst system therefor of the present invention is tin catalyst or organo-bismuth, preferred dibutyl tin dilaurate or 2 ethyl hexanoic acid bismuth.
The used water-removal additive of the present invention is the U.S. De of Angus chemical company oxazolidine water-removal additive Zoldine MS-PLus, and chemical name is 3-ethyl-2-methyl-2-(3-methylbutyl)-1, the 3-oxazolidine.
Second technical scheme that the present invention adopts is, a kind of method for preparing dual-component polyurethane adhesive is provided, and this method comprises: with listed as parts by weight; With styrene-grafted polyether glycol 300-800 part (preferred 500-700 part, more preferably 600 parts), W 166 PPG400 100-300 part (preferred 170-210 part; More preferably 195 parts) and W 166 PPG2000 100-300 part (preferred 170-210 part; More preferably 195 parts) mix, stirred 20-40 minute down at 60-80 ℃, obtain mixture; Skimmer 1-3 part (preferred 2 parts), catalyzer 1-3 part (preferred 2 parts) and water-removal additive 4-8 part (preferred 6 parts) join in the said mixture, continue down to stir 20-40 minute at 60-80 ℃; Cool to room temperature obtains the A component; With listed as parts by weight, with imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts) are mixed, and obtain the B component.
A component of the present invention and B component are packed respectively, during use A component and B group are mixed, and spreading upon then needs the adherent body surface.
The present invention is used to have screen material bonding of conductive ink layer, adopts above-mentioned technical scheme of the present invention, can obtain following beneficial effect at least:
1. the present invention is a solventless adhesive, solidifies the no any taste in back, compares environmental protection more with the solvent-laden sizing agent of tradition.
2. the present invention has good water resistance, is convenient to the adhering part washing.
3. the present invention has splendid initial adherence power and good toughness, and the material after bonding can be bent compression and place in the special framework, is convenient to simultaneously by the maintenance of doing over again of bonding PP material.
4. the present invention cooperates with electrically conductive ink, can produce the surface resistivity that meets customer demand.
Embodiment
Dual-component polyurethane adhesive of the present invention, as the A component, with imine modified 4,4 '-'-diphenylmethane diisocyanate and thick MDI are as the B component with the polyether glycol of different molecular weight.When this dual-component polyurethane adhesive cooperates with electrically conductive ink, can produce the surface resistivity that meets customer demand.
Specifically, dual-component polyurethane adhesive of the present invention has following several kinds of schemes:
A kind of dual-component polyurethane adhesive in weight part, comprises the A component: styrene-grafted polyether glycol 300-800 part (preferred 500-700 part; More preferably 600 parts); W 166 PPG400 100-300 part (preferred 170-210 part, more preferably 195 parts), W 166 PPG2000 100-300 part (preferred 170-210 part; More preferably 195 parts) and the selectivity additive 1-20 part (preferred 3-14 part) of adding; And B component: imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts).
A kind of preparation method of dual-component polyurethane adhesive comprises with listed as parts by weight, with styrene-grafted polyether glycol 300-800 part (preferred 500-700 part; More preferably 600 parts); W 166 PPG400100-300 part (preferred 170-210 part, more preferably 195 parts) and W 166 PPG2000 100-300 part (preferred 170-210 part, more preferably 195 parts) are mixed; Stirred 20-40 minute down at 60-80 ℃, obtain mixture; Skimmer 1-3 part (preferred 2 parts), catalyzer 1-3 part (preferred 2 parts) and water-removal additive 4-8 part (preferred 6 parts) join in the said mixture, continue down to stir 20-40 minute at 60-80 ℃; Cool to room temperature obtains the A component; With listed as parts by weight, with imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts) are mixed, and obtain the B component.
Through embodiment the present invention is done further detailed explanation below, but protection scope of the present invention is not limited to concrete embodiment.
Experiment material used among the embodiment is following:
Embodiment 1
With styrene-grafted polyether glycol 300kg, W 166 PPG400 100kg and W 166 PPG2000 100kg mix, and the speed with 100 rev/mins under 60 ℃ stirred 20 minutes, obtained mixture; Skimmer 1kg, catalyzer 1kg and water-removal additive 4kg are joined in the said mixture, and the speed with 100 rev/mins under 60 ℃ continues to stir 20 minutes; Cool to room temperature obtains the A component.With imine modified 4,4 '-'-diphenylmethane diisocyanate 600kg and thick MDI 200kg at room temperature mix with 100 rev/mins speed, obtain the B component.
Embodiment 2
With styrene-grafted polyether glycol 600kg, W 166 PPG400 195kg and W 166 PPG2000 195kg mix, and the speed with 100 rev/mins under 70 ℃ stirred 20 minutes, obtained mixture; Skimmer 2kg, catalyzer 2kg and water-removal additive 6kg are joined in the said mixture, and the speed with 100 rev/mins under 70 ℃ continues to stir 30 minutes; Cool to room temperature obtains the A component.With imine modified 4,4 '-'-diphenylmethane diisocyanate 700kg and thick MDI 300kg at room temperature mix with 100 rev/mins speed, obtain the B component.
Embodiment 3
With styrene-grafted polyether glycol 800kg, W 166 PPG400 300kg and W 166 PPG2000 300kg mix, and the speed with 100 rev/mins under 80 ℃ stirred 20 minutes, obtained mixture; Skimmer 3kg, catalyzer 3kg and water-removal additive 8kg are joined in the said mixture, and the speed with 100 rev/mins under 80 ℃ continues to stir 40 minutes; Cool to room temperature obtains the A component.With imine modified 4,4 '-'-diphenylmethane diisocyanate 800kg and thick MDI 400kg at room temperature mix with 100 rev/mins speed, obtain the B component.
Embodiment 4 performance tests
The present invention is in test environment conditions: temperature (25～28 ℃), humidity is carried out under (60～65%).
The preparation width is 5cm, and thickness is 0.8mm, and length is 12 of the PP film sheet materials of 30cm.The one side of 6 blocks of sheet materials is coated conductive ink layer therein, and final gained conductive ink layer is width 1cm, thickness 50 μ m, length 5cm.PP sheet material is the common sheet material in market.
A component and the B component of embodiment 1, embodiment 2 and embodiment 3 are mixed respectively, obtain polyurethane adhesive.
With 3 blocks of sheet materials that scribble electrically conductive ink wherein according to 0.8g/cm
2Usage quantity, the polyurethane adhesive of embodiment 1, embodiment 2 and embodiment 3 on the separate application, then respectively with the plate adhesion of three uncoated tackiness agent wherein on; Placing length at two of two boards material by the position of printing ink is the Copper Foil of 2cm; Wherein 1cm and printing ink join, and 1cm exposes as test lead, and these three groups of sheet materials are labeled as sample 1#; Sample 2#, sample 3#.
With three blocks of sheet materials that scribble electrically conductive ink of remainder according to 0.8g/cm
2Usage quantity, on the area of half block plank (15cm), be coated with the polyurethane adhesive of embodiment 1, embodiment 2 and embodiment 3 respectively, and respectively with the plate adhesion of remaining three uncoated electrically conductive inks on, be labeled as sample 4#, sample 5#, sample 6#.
Above-mentioned 6 samples are put into 80 ℃ of baking oven internal heating take out cooling 50 minutes after 30 minutes, then above-mentioned 6 samples are tested.
Initial sticking power test: adopt the two outstanding fraternal weight beams (200N LTZ type) of the U.S.; Testing standard is with reference to GB-T2791-1995 tackiness agent T peeling strength test method; To above-mentioned sample 4#; Sample 5#, sample 6# carry out initial bonding force test, and the result shows that initial bonding force is all greater than 1.0kgf/cm
2
The surface resistivity test: adopt U.S. ACL386 specific resistance tstr, testing method is carried out the test of surface resistivity with reference to the ASTMD-257 standard to sample 1#, sample 2#, sample 3#, and the result shows that sample 1#, sample 2#, sample 3# all are in 10
6～10
8Ω.
Embodiment 5
The present invention is in test environment conditions: temperature (25～28 ℃), humidity is carried out under (60～65%).
Water-fast test after the glue curing: according to the sample preparation methods of embodiment 4, prepare sample 1#, sample 2#, sample 3#, sample 4#, sample 5#, sample 6# again, above-mentioned sample was immersed in the tap water after 24 hours, dry.Sample 1#, sample 2#, sample 3# are carried out above-mentioned identical initial sticking power test, and the result shows that initial bonding force is greater than 1.0kgf/cm
2Sample 4#, sample 5#, sample 6# are carried out above-mentioned identical surface resistivity test, and the result shows that surface resistivity is in 10
6～10
8Ω.
But PP sheet material repair ability test: according to the sample preparation methods of embodiment 4, prepare sample 1#, sample 2#, sample 3# again, solidify after 24 hours, with hand with two peelable leaving of PP sheet material, plate surface not damaged.
Claims (7)
1. a dual-component polyurethane adhesive in weight part, comprises the A component: styrene-grafted polyether glycol 300-800 part (preferred 500-700; More preferably 600); W 166 PPG400 100-300 part (preferred 170-210, more preferably 195 parts), W 166 PPG2000 100-300 part (preferred 170-210; More preferably 195 parts) and the selectivity additive 1-20 part (preferred 3-14 part) of adding; And B component: imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts).
2. dual-component polyurethane adhesive according to claim 1; It is characterized in that; Said imine modified 4,4 '-'-diphenylmethane diisocyanate be contain 4,4 of carbodiimide and/or uretonimine groups '-diphenylmethanediisocyanate; NCO content is 20%-40%, and preferred NCO content is 29.5%.
3. dual-component polyurethane adhesive according to claim 1 is characterized in that, said thick MDI is polyphenyl polymethylene polyisocyanates and 4, the mixture of 4 '-'-diphenylmethane diisocyanate, and its functionality is 2.6～2.7; Wherein 4,4 '-'-diphenylmethane diisocyanate accounts for 40-60% (preferred 50%), and NCO content is 30%-32%.
4. according to each described dual-component polyurethane adhesive among the claim 1-3, it is characterized in that in weight part, said additive comprises skimmer 1-3 part (preferred 2 parts), catalyzer 1-3 part (preferred 2 parts) and water-removal additive 4-8 part (preferred 6 parts).
5. dual-component polyurethane adhesive according to claim 4 is characterized in that, said catalyzer is tin catalyst or organo-bismuth, preferred dibutyl tin dilaurate or 2 ethyl hexanoic acid bismuth.
6. dual-component polyurethane adhesive according to claim 4 is characterized in that, said water-removal additive is 3-ethyl-2-methyl-2-(3-methylbutyl)-1, the 3-oxazolidine.
7. one kind prepares the dual-component polyurethane adhesive method, and this method comprises: with listed as parts by weight, with styrene-grafted polyether glycol 300-800 part (preferred 500-700 part; More preferably 600 parts); W 166 PPG400 100-300 part (preferred 170-210 part, more preferably 195 parts) and W 166 PPG2000100-300 part (preferred 170-210 part, more preferably 195 parts) are mixed; Stirred 20-40 minute down at 60-80 ℃, obtain mixture; Skimmer 1-3 part (preferred 2 parts), catalyzer 1-3 part (preferred 2 parts) and water-removal additive 4-8 part (preferred 6 parts) are joined in the said mixture, continue down to stir 20-40 minute at 60-80 ℃; Cool to room temperature obtains the A component; With listed as parts by weight, with imine modified 4,4 '-'-diphenylmethane diisocyanate 600-800 part (preferred 700 parts) and thick MDI 200-400 part (preferred 300 parts) are mixed, and obtain the B component.
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| CN103665357A (en) * | 2014-01-07 | 2014-03-26 | 东北林业大学 | Polyester polyol containing lignin, preparing method thereof and polyurethane adhesive synthesized by same |
| CN103866961A (en) * | 2012-12-13 | 2014-06-18 | 飞虎(厦门)聚氨酯制品有限公司 | Composite material polyurethane rigid foam decorative marble pillar |
| CN104031240A (en) * | 2014-06-27 | 2014-09-10 | 无锡市崇安区科技创业服务中心 | Polyurethane adhesive and preparation method thereof |
| CN106318254A (en) * | 2016-08-23 | 2017-01-11 | 中山市鼎立森电子材料有限公司 | Bicomponent polyurethane protective film pressure-sensitive adhesive and synthetic process thereof |
| CN106349450A (en) * | 2016-09-29 | 2017-01-25 | 上海东大聚氨酯有限公司 | Portfolio polyether, polyurethane adhesive, raw material composition as well as preparation methods of portfolio polyether and polyurethane adhesive and application of polyurethane adhesive |
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| CN112175566A (en) * | 2020-09-28 | 2021-01-05 | 杭州应星新材料有限公司 | Room-temperature curing bi-component polyurethane heat-conducting composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106928895A (en) * | 2017-03-09 | 2017-07-07 | 宜兴市普利泰电子材料有限公司 | Flexible LED lamp bar polyurethane electronic casting glue and preparation method thereof |
| CN111517736A (en) * | 2020-04-29 | 2020-08-11 | 廊坊市辰阳保温材料有限公司 | Light non-combustible sound insulation board and preparation method thereof |
| CN111517736B (en) * | 2020-04-29 | 2022-02-11 | 廊坊市北辰创业树脂材料股份有限公司 | Light non-combustible sound insulation board and preparation method thereof |
| CN112175566A (en) * | 2020-09-28 | 2021-01-05 | 杭州应星新材料有限公司 | Room-temperature curing bi-component polyurethane heat-conducting composition and preparation method thereof |
| CN112175566B (en) * | 2020-09-28 | 2022-11-25 | 杭州应星新材料有限公司 | Room-temperature curing bi-component polyurethane heat-conducting composition and preparation method thereof |
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